Manufacturing method of laminates

Abstract

The present invention provides a method for manufacturing laminates that offers excellent productivity and superior adhesion of the decorative layer to the glass substrate. [Solution] The present invention provides a method for manufacturing a laminate comprising a glass substrate, an adhesive layer laminated on at least a portion of the glass substrate, and a decorative layer formed to be in contact with the adhesive layer. A decorative layer transfer step in which the decorative layer formed on the film substrate (a) is heated and transferred to one side of the temporary substrate, The process includes at least an adhesive layer transfer step of heating the adhesive layer formed on the film substrate (b) and transferring it onto the decorative layer.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a laminate.

Background Art

[0002] OLED (Organic light emitting diode) display devices have advantages in display performance such as high visibility, low viewing angle dependence, and fast response speed compared to liquid crystal display devices. In addition, since OLED display devices do not use a backlight, they are advantageous for thinning, and can also be used as flexible and foldable devices that can be curved or folded.

[0003] In an OLED display device, in order to impart functions such as surface protection and flexibility to the viewing side of the OLED element, a laminate having layers of various optical elements such as an adhesive layer, a substrate such as plastic or thin glass, and a hard coat layer is laminated.

[0004] In such a laminate, for example, in order to prevent external light from entering the OLED element, a decorative layer having reflectivity or light-shielding properties may be formed on the substrate. Since the decorative layer generally has low adhesion to thin glass, it is often formed by adhering to a plastic substrate, and the plastic substrate is laminated on the thin glass.

[0005] In recent years, thinning has been required for optical products such as OLED display devices. Therefore, attempts have been made to form a decorative layer directly on thin glass without using a plastic substrate (see Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

[0007] Patent Document 1 required exposure and drying after spin coating to form a decorative layer on thin glass, while Patent Document 2 required firing and drying after screen printing. However, the methods described in Patent Documents 1 and 2 required long drying / firing times for each sheet of thin glass, resulting in poor productivity. Furthermore, the adhesion of the decorative layer to the thin glass was insufficient.

[0008] The present invention has been made in view of the above problems, and its object is to provide a method for manufacturing a laminate that is excellent in productivity and also excellent in adhesion of the decorative layer to the glass substrate. [Means for solving the problem]

[0009] As a result of diligent research to achieve the above objective, the present inventors have found that a specific manufacturing method can produce a laminate that exhibits excellent productivity and superior adhesion of the decorative layer to the glass substrate.

[0010] The present invention provides a method for manufacturing a laminate comprising a glass substrate, an adhesive layer laminated on at least a portion of the glass substrate, and a decorative layer formed to contact the adhesive layer, comprising at least a decorative layer transfer step of heating the decorative layer formed on a film substrate (a) and transferring it to one side of a temporary substrate, and an adhesive layer transfer step of heating the adhesive layer formed on a film substrate (b) and transferring it onto the decorative layer.

[0011] In the present invention, the method for manufacturing a laminate preferably involves transferring the adhesive layer in the adhesive layer transfer step so as to cover the decorative layer.

[0012] In the present invention, it is preferable to perform the decorative layer transfer step and the adhesive layer transfer step in succession.

[0013] In the method for manufacturing the laminate of the present invention, it is preferable to perform the decorative layer transfer step and the adhesive layer transfer step while unwinding the temporary substrate from a wound body, and then winding the temporary substrate on which the decorative layer and the adhesive layer are laminated as a wound body.

[0014] In the method for manufacturing the laminate of the present invention, it is preferable that the amount of heat used when heating the adhesive layer during the transfer of the adhesive layer is smaller than the amount of heat used when heating the decorative layer during the transfer of the decorative layer.

[0015] Furthermore, the temporary substrate comprises a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer in this order, and it is preferable that the decorative layer is transferred onto the receiving layer in the decorative layer transfer step.

[0016] The present invention preferably includes a laminate transfer step in which one surface of the temporary substrate and one surface of the glass substrate are placed facing each other, the adhesive layer is brought into contact with the one surface of the glass substrate, heat lamination is performed while applying pressure from the side of the temporary substrate where the decorative layer and the adhesive layer are not laminated, and the laminate of the decorative layer and the adhesive layer is transferred onto the glass substrate.

[0017] Furthermore, the temporary substrate comprises a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer in this order, and in the laminate transfer process, it is preferable that the protective layer and the receiving layer in the temporary substrate are transferred onto the decorative layer together with the decorative layer and the adhesive layer when the decorative layer and the adhesive layer are transferred onto the glass substrate. [Effects of the Invention]

[0018] According to the method for manufacturing laminates of the present invention, it is possible to manufacture laminates that have excellent productivity and excellent adhesion of the decorative layer to the glass substrate. [Brief explanation of the drawing]

[0019] [Figure 1] A cross-sectional view showing an embodiment of a decorative layer transfer step in a method for manufacturing a laminate of the present disclosure. [Figure 2] A cross-sectional view showing an embodiment of an adhesive layer transfer step in a method for manufacturing a laminate of the present disclosure. [Figure 3] A cross-sectional view showing an embodiment of a laminate transfer step in a method for manufacturing a laminate of the present disclosure. [Figure 4] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 5] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 6] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 7] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 8] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 9] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 10] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 11] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 12] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention. [Figure 13] A cross-sectional view showing an embodiment of a laminate manufactured by the method for manufacturing a laminate of the present invention.

Embodiments for Carrying Out the Invention

[0020] In this specification, "adhesion" refers to the property of two surfaces adhering tightly to each other based on cohesive forces derived from the chemical structure of the composition in response to external pressure (e.g., minute pressure), and being able to be separated if necessary. In contrast, "bonding" refers to the property of two surfaces being firmly joined together by flow due to heating and subsequent solidification or curing due to cooling, etc., without exhibiting pressure-sensitive adhesion at room temperature and without the intention of separation.

[0021] Furthermore, in this specification, the form of the "adhesive" is not particularly limited and may be liquid at room temperature (for example, a fluid solid (paste), an adhesive composition, etc.), or a solid at room temperature. Also, the form of the "adhesive" is not particularly limited and may be in the form of a sheet. In this specification, the "adhesive layer" is a non-fluid sheet-like (layered) adhesive layer.

[0022] [Method for manufacturing laminates] The present invention relates to a method for manufacturing a laminate comprising a glass substrate, an adhesive layer laminated on at least a portion of the glass substrate, and a decorative layer formed to be in contact with the adhesive layer. The manufacturing method comprises at least the steps of: heating the decorative layer formed on a film substrate (a) and transferring it to one side of a temporary substrate (decorative layer transfer step); and heating the adhesive layer formed on a film substrate (b) and transferring it onto the decorative layer (adhesive layer transfer step). The present invention relates to the method for manufacturing a laminate and may hereafter be referred to as "the present invention's method for manufacturing a laminate." Furthermore, the laminate obtained by the present invention's method for manufacturing a laminate may be referred to as "the present invention's laminate."

[0023] Furthermore, the method for manufacturing the laminate of the present invention preferably includes a step of transferring the laminate, which includes the decorative layer and the adhesive layer, that is on the temporary substrate to the glass substrate (laminated substrate transfer step), and after the laminate transfer step, the method may also include a step of transferring the adhesive layer to the laminate (adhesive layer transfer step) and a step of attaching a release liner to the laminate (release liner attachment step).

[0024] The manufacturing method for the laminate of the present invention will be specifically described with reference to Figures 1 to 3. Note that the manufacturing method shown in Figures 1 to 3 is a preferred embodiment, and the manufacturing method for the laminate of the present invention is not limited to the above method.

[0025] <Decorative layer transfer process> In the decorative layer transfer process described above, as shown in Figure 1, the decorative layer 4 formed on the entire surface of the film substrate (a) 6 is heated and transferred to one side of the temporary substrate 7. Note that the decorative layer 4 does not need to be formed on the entire surface of the film substrate (a) 6, but may be formed on only a portion of the surface including the area to be transferred.

[0026] In the above decorative layer transfer process, first, the decorative layer 4 formed on the film substrate (a) 6 is placed facing the temporary substrate 7 (Figure 1(a)). Next, the decorative layer 4 is brought into contact with one side of the temporary substrate 7 (Figure 1(b)), and the decorative layer 4 can be transferred by heating from the side of the film substrate (a) 6 that does not have the decorative layer 4. Heating is performed selectively, selecting only the area of ​​the decorative layer 4 to be transferred. Heating can be performed using a known heating jig 8. In Figure 1(b), the decorative layer that has been heated selectively is shown as 4a. The temperature of the heating jig 8 during the above heating is appropriately selected depending on the type of decorative layer, and may be, for example, 60 to 300°C, or 80 to 250°C. After heating, the film substrate (a) 6 is peeled off from the temporary substrate 7, the selectively heated decorative layer 4 is transferred to the temporary substrate 7, and the unheated decorative layer 4 is peeled off from the temporary substrate 7 together with the film substrate (a) 6 (Figure 1(c)). Furthermore, considering applications such as preventing light from entering the interior when it has light-shielding properties, preventing light from leaking outside the housing, and concealing wiring, it is preferable that the decorative layer 4 be formed in an annular or frame-like shape.

[0027] The decorative layer described above preferably contains a heat-transferable resin. In this specification, "heat-transferable resin" is a resin in which a single layer of resin formed using the heat-transferable resin can be transferred to a substrate at a heating temperature (for example, at least one temperature between 60 and 250°C). The decorative layer may contain only one type of heat-transferable resin, or it may contain two or more types.

[0028] The above-mentioned heat-transferable resin preferably satisfies at least one of the following conditions: (1) the ratio of the elastic modulus at a heating temperature (for example, at least one temperature between 60 and 250°C) to the elastic modulus at 25°C [elastic modulus at heating temperature / elastic modulus at 25°C] is 1 / 5 or less, or (2) the softening point is between 0 and 200°C. Note that the above-mentioned elastic modulus is the storage modulus.

[0029] The ratio of the elastic moduli is more preferably 1 / 10 or less, and even more preferably 1 / 50 or less. When the ratio of the elastic moduli is 1 / 5 or less, the adhesive layer is not sticky at room temperature and can be handled easily, and when heated it becomes sticky and can be easily transferred to the substrate. The softening point can be measured by known or conventional measurement methods, such as the ring-and-ball method (JIS K7234), the mercury displacement method (JIS K7234), and the Vicat softening temperature (JIS K7206).

[0030] The above storage modulus is a value measured by dynamic viscoelasticity. The above storage modulus can be controlled by the type of base polymer constituting the above heat transferable resin, the monomer composition, the weight-average molecular weight, the amount of crosslinking agent used (amount added), and the type and content of other additives. If the above adhesive layer is curable, the elastic modulus of the adhesive layer in the above ratio may be the elastic modulus of the adhesive layer before curing or the elastic modulus of the adhesive layer after curing, but it is preferable to use the elastic modulus before heat transfer.

[0031] The above softening point is more preferably 20 to 200°C, and even more preferably 40 to 150°C. When the softening point is within the above range, it can be easily transferred to the substrate by heating. When the softening point is 0°C or higher, the adhesive layer is not sticky at room temperature and can be handled, resulting in excellent handling properties. When the softening point is 200°C or lower, stickiness can be generated by heating with low energy, allowing for energy-saving transfer to the substrate. If the adhesive layer is curable, the softening point of the adhesive layer may be the softening point of the adhesive layer before curing, or the softening point of the adhesive layer after curing. It is preferable that it be the softening point before heat transfer.

[0032] Examples of the above-mentioned heat-transferable resins include various polymers that exhibit rubber elasticity at room temperature, such as epoxy polymers, acrylic polymers, rubber polymers (natural rubber, synthetic rubber, mixtures thereof, etc.), polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluorine polymers. Only one of these heat-transferable resins may be used, or two or more may be used. In this specification, the above-mentioned polymers refer to those having monomer-derived structural units, and their weight-average molecular weight and number-average molecular weight are not particularly limited. For example, compounds with a weight-average molecular weight or number-average molecular weight of about 1000 are also included in the above-mentioned polymers.

[0033] The glass transition temperature (Tg) of the above-mentioned heat-transferable resin is preferably less than 200°C, more preferably 150°C or lower, and even more preferably 125°C or lower. The glass transition temperature is preferably, for example, -80°C or higher, more preferably -40°C or higher, and even more preferably -20°C or higher.

[0034] For the glass transition temperature (Tg) of a heat transfer resin, the theoretical glass transition temperature (Tg) can be obtained based on Fox's equation, as shown below. Fox's equation is a relationship between the glass transition temperature Tg of a polymer and the glass transition temperature Tgi of the homopolymer of the monomers constituting the polymer. In Fox's equation below, Tg represents the glass transition temperature (°C) of the polymer, Wi represents the weight fraction of monomer i constituting the polymer, and Tgi represents the glass transition temperature (°C) of the homopolymer formed from monomer i. For the glass transition temperature of the homopolymer, literature values ​​can be used. For example, "Polymer Handbook" (4th edition, John Wiley & Sons, Inc., 1999) lists the glass transition temperatures of various homopolymers. On the other hand, the glass transition temperature of the monomer homopolymer can also be determined by the method specifically described in Japanese Patent Publication No. 2007-51271. Fox's formula 1 / (273+Tg)=Σ[Wi / (273+Tgi)]

[0035] Examples of the heat-transferable resin in the decorative layer include those exemplified and described as the heat-transferable resin contained in the adhesive layer described above. The preferred embodiment of the heat-transferable resin in the decorative layer is the same as the preferred embodiment of the heat-transferable resin in the adhesive layer.

[0036] The decorative layer preferably contains the heat-transferable resin as a base polymer. The content of the base polymer in the decorative layer is not particularly limited, but is preferably 10% by mass or more (for example, 10 to 99.9% by mass) and more preferably 25% by mass or more (for example, 25 to 99.9% by mass) based on the total amount (100% by mass) of the decorative layer.

[0037] The decorative layer may contain a coloring agent. The coloring agent may be a dye or a pigment, as long as it is soluble or dispersible in the decorative layer. Pigments are preferred from the viewpoint of superior weather resistance and durability. One coloring agent may be used alone, or two or more may be used.

[0038] Examples of the above-mentioned colorants include black colorants, cyan colorants, magenta colorants, and yellow colorants. The above-mentioned colorants may be present in a single form or in a form containing two or more.

[0039] Examples of black colorants include carbon black, carbon nanotubes, graphite, copper oxide, manganese dioxide, azo pigments such as azomethine azoblack, aniline black, perylene black, titanium black, cyanine black, activated carbon, ferrite, magnetite, chromium oxide, iron oxide, molybdenum disulfide, complex oxide black pigments, anthraquinone-based organic black dyes, and azo-based organic black dyes. Examples of carbon black include furnace black, channel black, acetylene black, thermal black, and lamp black. Examples of black colorants include CI Solvent Black 3, 7, 22, 27, 29, 34, 43, and 70; CI Direct Black 17, 19, 22, 32, 38, 51, and 71; CI Acid Black 1, 2, 24, 26, 31, 48, 52, 107, 109, 110, 119, and 154; CI Disperse Black 1, 3, 10, and 24; and CI Pigment Black 1 and 7.

[0040] Examples of cyan-based colorants include CI Solvent Blue 25, 36, 60, 70, 93, 95; CI Acid Blue 6, 45; CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17, 17:1, 18, 22, 25, 56, 60, 63, 65, 66; CI Bat Blue 4, 60, CI Pigment Green 7, etc.

[0041] Examples of magenta-based colorants include CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Examples include Violet 1; CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28, etc. Furthermore, as a magenta-based colorant, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 42, 48:1 , 48:2, 48:3, 48:4, 49, 49:1, 50, 51, 52, 52:2, 53:1, 54, 55, 56, 57:1, 58, 60, 60:1, 63, 63:1, 63:2, 64, 64:1, 67, 68, 81, 83, 87, 88, 89, 90, 92, 10 1, 104, 105, 106, 108, 112, 114, 122, 123, 139, 144, 146, 147, 149, 150, 151, 163, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 19 Examples include 0, 193, 202, 206, 207, 209, 219, 222, 224, 238, and 245; CI Pigment Violet 3, 9, 19, 23, 31, 32, 33, 36, 38, 43, and 50; CI Bat Red 1, 2, 10, 13, 15, 23, 29, and 35.

[0042] Examples of yellow colorants include CI Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162; CI Pigment Orange 31, 43; CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 24, 34, 35, 37, 42, 53, 55, 65, 73, 74. Examples include 75, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 116, 117, 120, 128, 129, 133, 138, 139, 147, 150, 151, 153, 154, 155, 156, 167, 172, 173, 180, 185, 195; CI Bat Yellow 1, 3, 20, etc.

[0043] As the above-mentioned coloring agent, from the viewpoint of excellent light-shielding properties of the decorative layer, a coloring agent that produces black is preferred, that is, it is preferable to include a coloring agent so that the decorative layer produces black. As the above-mentioned coloring agent that produces black, a black-based coloring agent may be used, which is a combination of the above-mentioned black-based coloring agent or a coloring agent that produces a color other than black and functions as a black-based coloring agent.

[0044] The decorative layer described above may contain other components besides those listed above, as long as they do not impair the effects of the present invention. Examples of these other components include crosslinking agents, curing agents, curing catalysts, crosslinking accelerators, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers (metal powders, organic fillers, inorganic fillers, etc.), antioxidants, plasticizers, softeners, surfactants, antistatic agents, surface lubricants, leveling agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, rust inhibitors, granular materials, foil-like materials, flame retardants, silane coupling agents, ion trapping agents, and the like. Each of these other components may be used individually or in combination of two or more.

[0045] The thickness of the decorative layer is preferably 0.01 to 50 μm, more preferably 0.03 to 35 μm, and even more preferably 0.1 to 20 μm. If the thickness of the decorative layer is 0.01 μm or more, the light-shielding properties are superior when light-shielding is present. If the thickness of the decorative layer is 50 μm or less, the difference in height between the adhesive layer and the decorative layer is small, resulting in a good appearance. If the decorative layer is composed of multiple layers (a single layer formed by the contact of multiple layers), the above thickness is the total thickness of the multiple layers.

[0046] The film substrate (a) can be any material from which the decorative layer can be peeled off by heating, such as a plastic film. Examples of plastics that make up the plastic film include polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetylcellulose (TAC), polysulfone, polyarylate, polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and ethylene-propylene copolymer. One or more of these plastic materials may be used. Furthermore, since the film substrate (a) is heated in the decorative layer transfer process, it is preferable that it has heat resistance at the heating temperature during transfer, for example, that it does not deform and / or shrink.

[0047] Furthermore, the film substrate (a) may be a single layer or a multi-layered layer. If the film substrate (a) is a multi-layered layer, it may be a multi-layered layer comprising different plastic films, or a multi-layered layer comprising the same plastic film. Also, if the film substrate (a) is a multi-layered layer, it may include layers containing components other than the plastic films mentioned above, specifically, a release layer, a back layer, etc.

[0048] If the film substrate (a) has a release layer, it is preferable that the film substrate (a) has a release layer on the surface on which the decorative layer is laminated. By providing the above release layer, the decorative layer can be transferred more easily when transferring it to a temporary substrate. Specifically, the above release layer may include waxes, silicone wax, silicone resin, silicone-modified resin, fluororesin, fluoro-modified resin, polyvinyl alcohol, acrylic resin, polyester resin, thermocrosslinkable epoxy-amino resin, and thermocrosslinkable alkyd-amino resin. Each component in the above release layer may be used individually or in combination of two or more.

[0049] There are no particular limitations on the method for forming the above-mentioned release layer. The release layer can be prepared by dissolving or dispersing each of the above-mentioned components in a suitable solvent, applying this coating solution to one surface of a film substrate (a), and drying and curing the resulting composition layer. Alternatively, the release layer can be applied to a release liner, the resulting composition layer can be cured by irradiating it with active energy rays, and then transferred onto the film substrate (a). Furthermore, if necessary, it may be further heated and dried.

[0050] The thickness of the above-mentioned peeling layer is not particularly limited, but 0.1 to 5 μm is preferred.

[0051] Furthermore, if the film substrate (a) has a back layer, it is particularly preferable to have the back layer on the side opposite to the side on which the decorative layer is laminated. By having a back layer on the side opposite to the decorative layer, the heat resistance of the film substrate (a) can be improved. Specifically, the back layer may include resin components such as polyester, polyacrylic acid ester, polyvinyl acetate, styrene acrylate resin, polyurethane, polyethylene, polypropylene, polyolefins, polystyrene, polyvinyl chloride, polyether, polyamide, polyimide, polyamide-imide, polycarbonate, polyacrylamide, polyvinyl chloride, polyvinyl butyral, polyvinyl acetal, and silicone-modified versions thereof, as well as various additives to improve slip properties, such as release agents such as wax, higher fatty acid amide, phosphate ester compounds, metal soap, silicone oil, and surfactants, organic powders such as fluororesins, and inorganic particles such as silica, clay, talc, and calcium carbonate.

[0052] There are no particular limitations on the method for forming the back layer described above. The back layer can be prepared by dissolving or dispersing each of the above components in a suitable solvent, applying this coating solution to one side of a film substrate (a), and drying and curing the resulting composition layer. Alternatively, the back layer coating solution can be applied to a release liner, the resulting composition layer can be cured by irradiating it with active energy rays, and then transferred onto the film substrate (a). Furthermore, if necessary, it may be further heated and dried.

[0053] The thickness of the back layer is not particularly limited, but from the viewpoint of providing sufficient heat resistance, 0.01 to 5 μm is preferred.

[0054] The decorative layer described above can be formed on a film substrate (a) by known or conventional methods. For example, the decorative layer can be produced by coating a composition for forming the decorative layer onto a film substrate (a) and drying and curing the resulting composition layer, or by coating the composition onto a release liner, curing the resulting composition layer by irradiating it with active energy rays, and then transferring it onto a film substrate (a). If necessary, it may also be further heated and dried.

[0055] For coating the above composition, known coating methods may be used. For example, coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, direct coaters, and die coaters may be used.

[0056] <Adhesive layer transfer process> In the adhesive layer transfer process described above, as shown in Figure 2, the adhesive layer 3 formed on the film substrate (b) 9 is heated and transferred onto the decorative layer 4 formed on one side of the temporary substrate 7. In the adhesive layer transfer process described above, it is preferable to transfer the adhesive layer 3 so as to cover the entire surface of the decorative layer 4. Note that the adhesive layer 3 does not necessarily have to be formed over the entire surface of the film substrate (b) 9, but may be formed in a part of the area including the area to be transferred. When the adhesive layer 3 is heat-transferred onto the decorative layer 4, in particular, if the heat-transferable resin contained in the adhesive layer 3 and the heat-transferable resin contained in the decorative layer 4 are of the same type, the area near the boundary between the decorative layer 4 and the adhesive layer 3 will be compatible, resulting in excellent adhesion between the adhesive layer 3 and the decorative layer 4, and as a result, excellent adhesion of the decorative layer 4 to the glass substrate 2.

[0057] In the adhesive layer transfer process described above, first, the adhesive layer 3 formed on the film substrate (b) 9 is brought into contact with the side of the temporary substrate 7 that has the decorative layer 4 (Figure 2(a)). Next, the adhesive layer 3 is brought into contact with the decorative layer 4 on the temporary substrate 7 (Figure 2(b)), and heating can be performed from the side of the film substrate (b) 9 that does not have the adhesive layer 3. The heating is performed selectively, selecting only the area of ​​the adhesive layer 3 to be transferred. Heating can be performed using a known heating jig 10. In Figure 2(b), the adhesive layer that has been heated selectively is shown as 3a. The temperature of the heating jig 10 during the above heating is appropriately selected depending on the type of adhesive layer, and may be, for example, 60 to 300°C, or 80 to 250°C. After heating, the film substrate (b) 9 is peeled off from the temporary substrate 7, the selectively heated adhesive layer 3 is transferred onto the decorative layer 4, and the unheated adhesive layer 3 is peeled off from the temporary substrate 7 together with the film substrate (b) 9 (Figure 2(c)).

[0058] It is preferable that the amount of heat used when heating during the transfer of the adhesive layer 3 is less than the amount of heat used when heating during the transfer of the decorative layer 4. In this case, when the adhesive layer 3 is brought into contact with the decorative layer 4 and the film substrate (b) 9 is peeled off, the so-called reverse transfer of the decorative layer 4, where the heated layer 4 is transferred to the adhesive layer 3 and then to the film substrate (b) 9, can be suppressed.

[0059] After transferring the adhesive layer 3, the adhesive layer 3 may be cured. Curing may be performed before the next step, after any of the subsequent steps, or all at once if there are multiple adhesive layers 3. The curing operation is appropriately selected according to the type of curability of the adhesive layer described above.

[0060] (adhesive layer) The adhesive layer preferably contains a heat-transferable resin. The adhesive layer may contain only one type of heat-transferable resin, or it may contain two or more types.

[0061] Examples of the heat-transferable resin in the adhesive include those exemplified and described as the heat-transferable resin contained in the decorative layer described above. The preferred embodiment of the heat-transferable resin in the adhesive layer is the same as the preferred embodiment of the heat-transferable resin in the decorative layer.

[0062] The adhesive layer preferably contains the heat-transferable resin as a base polymer. The content of the base polymer in the adhesive layer is not particularly limited, but is preferably 75% by mass or more (for example, 75 to 99.9% by mass) and more preferably 85% by mass or more (for example, 85 to 99.9% by mass) based on the total amount (100% by mass) of the adhesive layer.

[0063] The heat-transferable resin in the adhesive layer may be the same type as the heat-transferable resin contained in the decorative layer (for example, acrylic polymer and acrylic polymer), or it may be a different type (for example, acrylic polymer and rubber polymer). If they are the same type, when the adhesive layer is heat-transferred onto the decorative layer, the area near the boundary between the decorative layer and the adhesive layer becomes compatible, resulting in excellent adhesion between the adhesive layer and the decorative layer, and consequently, excellent adhesion of the decorative layer to the substrate.

[0064] The adhesive layer described above preferably has curability. Examples of curability include active energy ray curability, thermosetting, and moisture curability. Examples of active energy rays include ionizing radiation such as alpha rays, beta rays, gamma rays, neutron rays, and electron beams, as well as ultraviolet rays.

[0065] The adhesive layer may contain a curable resin. Examples of curable resins include active energy ray curable resins, thermosetting resins, and moisture-curable resins. The adhesive layer may contain only one type of curable resin, or two or more types. The heat transfer resin may also be curable. That is, the heat transfer resin may be a curable resin. A heat transfer resin with curability may be included in the content of either the heat transfer resin or the thermosetting resin.

[0066] As the active energy ray curable resin mentioned above, known or conventional active energy ray curable resins can be used, for example, resins having active energy ray curable functional groups. Examples of the active energy ray curable functional groups include epoxy group-containing groups such as glycidyl groups, and ethylenically unsaturated groups such as allyl groups, acryloyl groups, and methacryloyl groups. The active energy ray curable functional group may be one type or two or more types.

[0067] Examples of the above-mentioned active energy ray curable resins include resins having two or more of the above-mentioned active energy ray curable functional groups in one molecule, such as epoxy resins, polyester acrylic resins, polyether acrylic resins, urethane acrylic resins, carbonate acrylic resins, epoxy acrylic resins, and other acrylic resins.

[0068] The above-mentioned thermosetting resin can be any known or conventional thermosetting resin, for example, a resin having a thermosetting functional group. Examples of the above-mentioned thermosetting functional group include epoxy group-containing groups such as glycidyl groups, carboxyl groups, hydroxyl groups, isocyanate groups, aziridyl groups, and the like. The above-mentioned thermosetting functional group may be one type or two or more types.

[0069] Examples of the thermosetting resins mentioned above include epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyester resins, bismaleimide resins, polyurethane resins, diallyl phthalate resins, silicone resins, polyimide resins, polyamideimide resins, and benzocyclobutene resins.

[0070] The adhesive layer described above may contain other components besides those listed above, as long as they do not impair the effects of the present invention. Examples of these other components include crosslinking agents, curing agents, curing catalysts, crosslinking accelerators, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers (metal powders, organic fillers, inorganic fillers, etc.), colorants (pigments, dyes, etc.), antioxidants, plasticizers, softeners, surfactants, antistatic agents, surface lubricants, leveling agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, rust inhibitors, granular materials, foil-like materials, flame retardants, silane coupling agents, ion trapping agents, and the like. Each of these other components may be used individually or in combination of two or more.

[0071] The thickness of the adhesive layer is preferably 0.01 to 50 μm, more preferably 0.03 to 35 μm, and even more preferably 0.1 to 20 μm. When the thickness of the adhesive layer is 0.01 μm or more, the adhesion of the decorative layer to the substrate is superior. When the thickness of the adhesive layer is 50 μm or less, the difference in height between the adhesive layer and the decorative layer is small, resulting in a good appearance. If the adhesive layer is composed of multiple layers (a single layer formed by the contact of multiple layers), the above thickness is the total thickness of the multiple layers. Furthermore, the thickness of the adhesive layer is the thickness of the adhesive layer located between the substrate and the decorative layer. For example, as shown in Figure 8, if the adhesive layer covers the decorative layer, it is the thickness of the adhesive layer 3 located between the glass substrate 2 and the decorative layer 4.

[0072] As the film substrate (b), those exemplified and described above as film substrate (a) can be used. Furthermore, since the film substrate (b) is heated in the adhesive layer transfer process, it is preferable that it has heat resistance at the heating temperature during transfer, for example, that it does not deform and / or shrink.

[0073] The adhesive layer described above can be formed on the film substrate (b) by known or conventional methods. For example, the adhesive layer can be produced by coating the film substrate (b) with a composition for forming an adhesive layer (adhesive composition) and drying and curing the resulting adhesive composition layer, or by coating the adhesive composition onto a release liner, curing the resulting adhesive composition layer by irradiating it with active energy rays, and then transferring it onto the film substrate (b). If necessary, it may also be further heated and dried.

[0074] A known coating method may be used for applying (coating) the above adhesive composition. For example, coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, direct coaters, and die coaters may be used.

[0075] The ratio of the thickness of the adhesive layer to the thickness of the decorative layer [thickness of adhesive layer:thickness of decorative layer] is preferably 1:0.01 to 1:100, more preferably 1:0.015 to 1:67, and even more preferably 1:0.02 to 1:50. If the thickness of the adhesive layer is greater than 1:100, the thickness of the adhesive layer is sufficient relative to the thickness of the decorative layer, resulting in superior adhesion of the decorative layer to the glass substrate. If the thickness of the decorative layer is less than 1:100, the difference in height between the adhesive layer and the decorative layer is small, resulting in a better appearance. If the thickness of the decorative layer is greater than 1:0.01, the light-shielding properties are superior if light-shielding properties are present. If the thickness of the adhesive layer is less than 1:0.01, the difference in height between the adhesive layer and the decorative layer is small, resulting in a better appearance. Note that if the adhesive layer and the decorative layer are each composed of multiple layers (a single layer formed by the contact of multiple layers), the above thickness is the total thickness of the multiple layers. Furthermore, the adhesive layer and decorative layer in the above ratio are layers provided on the same side of the substrate, that is, the thickness of the adhesive layer and decorative layer formed on one of the surfaces (for example, the thickness of adhesive layer 3 and decorative layer 4 in Figures 4-7). Also, the thickness of the adhesive layer in the above ratio is the thickness of the adhesive layer located between the substrate and the decorative layer, for example, if the adhesive layer covers the decorative layer as shown in Figure 8, it is the thickness of adhesive layer 3 located between the glass substrate 2 and the decorative layer 4.

[0076] As the temporary substrate mentioned above, the same type of plastic film as exemplified and described as the film substrate (a) above can be used. The temporary substrate may be single-layered or multi-layered. If the temporary substrate is multi-layered, it is preferable that it comprises, in this order, a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer. The temporary substrate may also comprise other layers besides the plastic film, release layer, protective layer, and receiving layer, but it is preferable that the receiving layer is formed on the outermost surface of the temporary substrate.

[0077] As the release layer, the example and described above can be used as the release layer of the film substrate (a).

[0078] There are no particular limitations on the method for forming the above-mentioned release layer. The release layer can be prepared by dissolving or dispersing each of the above-mentioned components in a suitable solvent, applying and drying this coating solution on one surface of a temporary substrate, and then drying and curing the resulting composition layer. Alternatively, the release layer can be applied (coated) onto a release liner, the resulting composition layer can be cured by irradiating it with active energy rays, and then transferred onto a temporary substrate. Furthermore, if necessary, it may be further heated and dried.

[0079] The protective layer described above is provided to improve peelability when transferring the decorative layer and adhesive layer from the temporary substrate, and to protect the decorative layer after peeling. Because the adhesion between the protective layer and the release layer is relatively small, it is possible to easily separate the protective layer and the release layer during the laminate transfer process described later.

[0080] The protective layer described above may be the specific example and description of the release layer. The protective layer may have the same composition as the release layer, but it is preferable that it has a different composition.

[0081] There are no particular limitations on the method for forming the protective layer described above. The protective layer can be prepared by dissolving or dispersing each of the above components in a suitable solvent, applying and drying this coating solution on one surface of the release layer to dry and harden the resulting composition layer, or by applying (coating) the protective layer coating solution onto a release liner, irradiating the resulting composition layer with active energy rays to harden it, and then transferring it onto the release layer. If necessary, further heating and drying may be performed.

[0082] The receiving layer has excellent adhesion to the decorative layer and preferably contains a resin component (particularly a thermoplastic resin). Specifically, examples include polyolefins such as polypropylene, halogenated resins such as polyvinyl chloride or polyvinylidene chloride, vinyl resins such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer or polyacrylic acid ester, polyesters such as polyethylene terephthalate or polybutylene terephthalate, polystyrene, polyamide, ethylene, or copolymers of olefins such as propylene with other vinyl polymers, ionomers, or cellulose resins such as cellulose diastase, polycarbonate, epoxy resin, and the like.

[0083] There are no particular limitations on the method for forming the above-mentioned receiving layer. The receiving layer can be prepared by dissolving or dispersing each of the above-mentioned components in a suitable solvent, applying and drying this coating solution onto one surface of the protective layer to dry and harden the resulting composition layer, or by applying (coating) the above-mentioned receiving layer coating solution onto a release liner, irradiating the resulting composition layer with active energy rays to harden it, and then transferring it onto the protective layer. Furthermore, if necessary, it may be further heated and dried.

[0084] The thickness of the receiving layer is not particularly limited, but 1 to 10 μm is preferred from the viewpoint of exhibiting sufficient heat resistance.

[0085] <Laminate Transfer Process> In the laminate transfer process described above, as shown in Figure 3, the laminate of the decorative layer 4 and adhesive layer 3 formed on the temporary substrate 7 is heated and transferred onto the glass substrate 2. Specifically, in the laminate transfer process, first, the side of the temporary substrate 7 on which the decorative layer 4 and adhesive layer 3 are formed is placed facing one side of the glass substrate 2 (Figure 3(a)). Next, the adhesive layer 3 is brought into contact with one side of the glass substrate 2 (Figure 3(b)). Then, heat lamination is performed while applying pressure with a roll 11 from the side of the temporary substrate 7 that does not have the decorative layer 4 and adhesive layer 3. After that, the temporary substrate 7 is peeled off from the glass substrate 2 and the decorative layer 4 and adhesive layer 3 are transferred onto the glass substrate 2 (Figure 3(c)). Alternatively, the transfer may be performed by heat pressing instead of heat lamination. In this way, the laminate 1 shown in Figure 4 can be manufactured.

[0086] The pressure used during the heat lamination process is appropriately selected depending on the type of glass substrate, decorative layer, and adhesive layer, and is preferably 0.05 to 10 MPa. The heating temperature may be 60 to 250°C or 80 to 200°C. The lamination speed is not particularly limited and is appropriately adjusted depending on the type of glass substrate, decorative layer, and adhesive layer used, but may be 0.01 m / min to 10 m / min.

[0087] (Glass substrate) The glass substrate mentioned above is not particularly limited, but it is preferably chemically strengthened glass or alkali-free glass. Furthermore, the glass substrate can be thin. For example, ultra-thin glass can be used.

[0088] Alkali-free glass refers to glass that contains less alkali components (e.g., alkali metal oxides such as Na2O and K2O) than conventional alkali glass. However, alkali-free glass also includes glass that contains only trace amounts of alkali components. In this specification, the alkali component (alkali metal oxide) content in alkali-free glass may be, for example, 1% by mass or less, 0.1% by mass or less, or 0.05% by mass or less, or it may be substantially free of alkali components. Here, "substantially free" means that it is not contained except for unavoidable impurities.

[0089] Chemically strengthened glass offers superior bending resistance and impact resistance compared to unstrengthened glass. Furthermore, chemically strengthened glass possesses excellent mechanical strength, allowing for the use of thinner glass.

[0090] Chemically strengthened glass is glass whose mechanical properties have been enhanced by chemical means through ion exchange near the glass surface, and it has a compressive stress layer on its surface. Chemically strengthened glass has a high potassium content on its surface, resulting in compressive stress on the surface. For example, by performing ion exchange at a temperature below the glass transition temperature, alkali metal ions with small ionic radii (e.g., lithium ions, sodium ions) on the glass surface are replaced with other alkali ions with larger ionic radii (e.g., sodium ions, potassium ions). This leaves compressive stress on the glass surface, improving the strength of the glass.

[0091] Chemically strengthened glass typically has a rectangular parallelepiped shape, or a hexahedron. Chemically strengthened glass has two faces (first and second principal faces) and four sides. Typically, chemically strengthened glass is hexahedral glass, where all faces are chemically strengthened. Hexahedral glass can be obtained, for example, by chemically strengthening a glass plate. Alternatively, chemically strengthened glass may be 2-sided glass, obtained by cutting hexahedral glass to a desired size.

[0092] Examples of glass materials that make up chemically strengthened glass include aluminosilicate glass, soda-lime glass, borosilicate glass, lead glass, alkali barium glass, and aluminoborsilicate glass.

[0093] Chemically strengthened glass has a higher potassium ion concentration on its surface than near the center in the thickness direction. Therefore, glass can be identified as chemically strengthened glass by the following method. For example, if the glass is divided into 10 sections in the thickness direction, and the potassium ion concentrations in each section are labeled d1, d2, d3, ..., d10 from the outermost surface, then the glass can be identified as chemically strengthened glass if the potassium ion concentrations satisfy both d1 > d5 and d10 > d5. The potassium concentration distribution in the thickness direction can be measured, for example, by energy-dispersive X-ray analysis (EDX). Specifically, EDX mapping can be performed on the side surface of the glass substrate in the thickness direction using Oxford Instruments' "X-MaxN" at an acceleration voltage of 10 kV to quantify the potassium concentration.

[0094] As chemically strengthened glass, ultra-thin glass can be used. Commercially available chemically strengthened glass can be used as appropriate, for example, Corning's "Gorilla Glass," and as ultra-thin glass, examples include SCHOTT's "SCHOTT UTG," Corning's "Willow Glass," and Nippon Electric Glass Co., Ltd.'s "Dinorex UTG."

[0095] The thickness of the glass substrate (thickness of chemically strengthened glass or alkali-free glass) is preferably 10 to 2000 μm, more preferably 15 to 1000 μm, and even more preferably 20 to 500 μm, from the viewpoint of excellent flexibility and impact resistance.

[0096] Furthermore, if the temporary substrate comprises a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer in this order, it is preferable that the protective layer and the receiving layer are transferred onto the decorative layer when the decorative layer and the adhesive layer are transferred onto the glass substrate. The presence of the protective layer and the receiving layer on the decorative layer protects the decorative layer. Also, if the adhesive layer is in contact with the receiving layer, the protective layer and the receiving layer may be transferred onto the adhesive layer.

[0097] Here, when the laminate of the adhesive layer 3 and the decorative layer 4 is transferred onto the glass substrate 2, in particular, if the heat transferable resin contained in the adhesive layer 3 and the heat transferable resin contained in the decorative layer 4 are of the same type, the area near the boundary between the decorative layer 4 and the adhesive layer 3 becomes compatible, resulting in excellent adhesion between the adhesive layer 3 and the decorative layer 4, and consequently, excellent adhesion of the decorative layer 4 to the glass substrate 2.

[0098] When manufacturing a laminate 1 in which the decorative layer 4 is multilayered, as shown in Figure 5, the decorative layer transfer step may be performed multiple times in succession. Also, when manufacturing a laminate 1 in which the adhesive layer 3 is formed over the entire surface, as shown in Figure 6, the adhesive layer 3 can be transferred to the entire surface of the temporary substrate 7 by heating the entire surface of the film substrate (b) 9 in the adhesive layer transfer step. Furthermore, when manufacturing a laminate 1 in which the adhesive layer 3 is provided on both sides of the glass substrate 2, as shown in Figure 7, the adhesive layer 3 on the film substrate (b) 9 obtained by the adhesive layer transfer step can be transferred to the other surface of the substrate in the same manner as in the laminate transfer step, either after the laminate transfer step or before the decorative layer transfer step, thereby forming the adhesive layer 3 on the other surface of the glass substrate 2. Furthermore, when manufacturing a laminate 1 in which the adhesive layer 3 covers the decorative layer 4, as shown in Figure 8, the laminate can be manufactured by performing the laminate transfer step on a laminate obtained by going through the adhesive layer transfer step, which selectively transfers the adhesive layer, the decorative layer transfer step, and the adhesive layer transfer step, which transfers the adhesive layer to the entire surface of the temporary substrate, in that order.

[0099] <Adhesive layer transfer process> If the laminate of the present invention includes an adhesive layer as shown in Laminate 1 in Figures 9 to 13, the method for manufacturing the laminate of the present invention may include a step of transferring the adhesive layer to a substrate (adhesive layer transfer step) after the laminate transfer step.

[0100] (Adhesive layer) The adhesive layer can be a known or conventional adhesive layer. Preferably, the adhesive layer is a solvent-free adhesive layer containing a photopolymerized polymer as the base polymer. Such an adhesive layer can be manufactured from a solvent-free adhesive composition. When manufacturing the adhesive layer from a solvent-free adhesive composition, there is no need to remove the solvent by volatilizing it from the coating film of the composition. Therefore, a laminate comprising the adhesive layer is suitable for reducing environmental impact.

[0101] The adhesive layer is preferably a sheet-like pressure-sensitive adhesive (solvent-free adhesive sheet) formed from a solvent-free adhesive composition. Therefore, the adhesive layer (solvent-free adhesive composition) preferably contains at least a photopolymerizable polymer as a base polymer. A photopolymerizable polymer is a polymer formed by a polymerization method in which the polymerization reaction of polymerizable components is advanced by irradiation with active energy rays such as ultraviolet light.

[0102] The base polymer is an adhesive component that exhibits tackiness in the adhesive layer described above. The base polymer is not particularly limited, but examples include acrylic polymers, rubber polymers (such as natural rubber polymers and synthetic rubber polymers), silicone polymers, polyester polymers, urethane polymers, polyamide polymers, epoxy polymers, vinyl alkyl ether polymers, and fluorine polymers. One type of base polymer may be used, or two or more types may be used.

[0103] The content of the base polymer in the adhesive layer is not particularly limited, but is preferably 75% by mass or more (for example, 75 to 99.9% by mass) and more preferably 85% by mass or more (for example, 85 to 99.9% by mass) based on the total amount (100% by mass) of the adhesive layer.

[0104] The adhesive layer described above may contain other components besides those listed above, as long as they do not impair the effects of the present invention. Examples of these other components include crosslinking agents, curing agents, curing catalysts, crosslinking accelerators, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers (metal powders, organic fillers, inorganic fillers, etc.), colorants (pigments, dyes, etc.), antioxidants, plasticizers, softeners, surfactants, antistatic agents, surface lubricants, leveling agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, rust inhibitors, granular materials, foil-like materials, flame retardants, silane coupling agents, ion trapping agents, and the like. Each of these other components may be used individually or in combination of two or more.

[0105] The thickness of the adhesive layer is preferably 5 to 2500 μm, more preferably 10 to 1000 μm, and even more preferably 15 to 500 μm. When the thickness of the adhesive layer is 5 μm or more, the adhesion to the substrate and the decorative layer is superior. When the thickness of the adhesive layer is 2500 μm or less, when the substrate is bent, the formation of creases due to deformation of the adhesive layer is less likely to occur. If the adhesive layer is composed of multiple layers (a single layer formed by the contact of multiple layers), the above thickness is the total thickness of the multiple layers.

[0106] The ratio of the total thickness of the adhesive layer and decorative layer to the thickness of the adhesive layer [(thickness of adhesive layer + thickness of decorative layer):thickness of adhesive layer] is preferably 1:0.5 to 1:2500, more preferably 1:1 to 1:1500, and even more preferably 1:2 to 1:1000. If the thickness of the adhesive layer is greater than 1:0.5, it can adequately follow the steps between the adhesive layer and the decorative layer. If the thickness of the adhesive layer is less than 1:2500, adhesive overflow and blocking between laminates can be further suppressed. Note that if the adhesive layer, decorative layer, and adhesive layer are each composed of multiple layers (a single layer formed by the contact of multiple layers), the above thickness is the total thickness of the multiple layers. Furthermore, the adhesive layer, decorative layer, and tack layer in the above ratio are layers provided on the same side of the substrate, that is, the thickness of the adhesive layer, decorative layer, and tack layer formed on one of the above sides (for example, the thickness of adhesive layers 31, 32, decorative layer 4, and tack layers 51, 52 in Figures 12 and 13). Also, the thickness of the adhesive layer in the above ratio is the thickness of the adhesive layer located between the substrate and the decorative layer, for example, if the adhesive layer covers the decorative layer as shown in Figure 8, it is the thickness of the adhesive layer 31 located between the glass substrate 2 and the decorative layer 4.

[0107] The above-mentioned adhesive layer can be manufactured, for example, by applying an adhesive composition for forming the adhesive layer onto a release liner and drying and curing the resulting adhesive composition layer, or by applying the above-mentioned adhesive composition onto a release liner and curing the resulting adhesive composition layer by irradiating it with active energy rays. Furthermore, if necessary, it may be further heated and dried.

[0108] Known coating methods may be used for applying (coating) the above adhesive composition. For example, coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, direct coaters, and die coaters may be used.

[0109] In the adhesive layer transfer process described above, the adhesive layer formed on the release liner is transferred onto the substrate. Specifically, in the adhesive layer transfer process, first, the adhesive layer formed on the release liner is placed facing one side of the substrate. Next, the adhesive layer is brought into contact with one side of the substrate. Then, lamination is performed by applying pressure with a roll from the side of the release liner that does not have the adhesive layer. Heating may be applied during lamination. After that, the release liner is peeled off the substrate, and the adhesive layer is transferred onto the substrate.

[0110] <Release Liner Application Process> A release liner may be attached to the laminate of the present invention obtained as described above (release liner attachment step). The release liner may be attached to one side of the laminate of the present invention, or to both sides, or one release liner with both sides being release surfaces may be attached to one side.

[0111] The above-mentioned release liner can be any conventional release paper, and is not particularly limited, but examples include a substrate having a release treatment layer, a low-adhesion substrate made of a fluoropolymer, or a low-adhesion substrate made of a nonpolar polymer. Examples of substrates having a release treatment layer include plastic films and paper surface-treated with release agents such as silicone-based, long-chain alkyl-based, fluorine-based, and molybdenum sulfide. Examples of fluorine-based polymers in the low-adhesion substrate made of a fluoropolymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene-vinylidene fluoride copolymer. Examples of nonpolar polymers include olefin resins (e.g., polyethylene, polypropylene, etc.). The release liner can be formed by known or conventional methods. The thickness of the release liner is also not particularly limited.

[0112] Furthermore, in the method for manufacturing the laminate of the present invention, it is preferable to perform the decorative layer transfer step and the adhesive layer transfer step continuously, and it is more preferable to perform the decorative layer transfer step and the adhesive layer transfer step by roll-to-roll. Specifically, the decorative layer transfer step and the adhesive layer transfer step are performed while unwinding from a wound body in which the temporary substrate is wound, and the temporary substrate on which the decorative layer and the adhesive layer are laminated is wound up, thereby obtaining a temporary substrate on which the decorative layer and the adhesive layer are laminated as a wound body. Using the laminate containing the obtained temporary substrate and a glass substrate, the laminate transfer step, and optionally the adhesive layer transfer step and / or the release liner application step are performed to obtain a laminate comprising a glass substrate, an adhesive layer laminated on at least a part of the glass substrate, and a decorative layer formed to contact the adhesive layer. In this case, the order and number of times the decorative layer transfer step and the adhesive layer transfer step are appropriately selected depending on the layer configuration of the laminate. Furthermore, the laminate of film substrate (a) and decorative layer, and the laminate of film substrate (b) and adhesive layer, provided in the roll-to-roll process, may each be unwound from a wound state, and after each of the above steps, film substrate (a), film substrate (b), and temporary substrate may be wound up to form a wound body.

[0113] The present invention's method for manufacturing laminates allows for the continuous transfer of the decorative layer and the adhesive layer, resulting in superior yield and improved productivity compared to conventional methods that required drying and firing steps. In addition, while conventional methods required a step to remove organic solvents, the present invention's method for manufacturing laminates can be carried out without solvents, resulting in a lower environmental impact.

[0114] While alkali glass is commonly used for glass sheets, its hydrophilic surface allows for the formation of highly adhesive decorative layers to the glass using conventional printing methods such as screen printing. However, chemically strengthened glass and alkali-free glass, although thin, have high strength and excellent bending resistance. Their smooth and highly hydrophobic surfaces make it difficult to form highly adhesive decorative layers to them using conventional printing methods such as screen printing. In contrast, laminates manufactured using the lamination manufacturing method of the present invention contain a heat-transferable resin in both the decorative layer and the adhesive layer. This results in excellent adhesion between the adhesive layer, the decorative layer, and the adhesive layer to chemically strengthened glass and alkali-free glass, which have smooth and highly hydrophobic surfaces, making it difficult for each layer to detach from the chemically strengthened glass and alkali-free glass. Furthermore, the decorative layer of the laminate of the present invention is less likely to detach from the chemically strengthened glass and alkali-free glass when subjected to impact or repeated bending. Furthermore, while screen printing requires coating the glass and subsequent drying and firing processes, the laminate of the present invention can be manufactured using a method other than screen printing. Therefore, drying and firing processes are unnecessary, resulting in efficient and energy-saving manufacturing. Moreover, while screen printing typically forms an adhesive layer only partially, the laminate of the present invention allows for the formation of an adhesive layer over the entire surface of the chemically strengthened glass and alkali-free glass substrates. In this case, the adhesion between the adhesive layer and the chemically strengthened glass and alkali-free glass can be improved.

[0115] (Laminated structure) The laminate provided by the manufacturing method of the present invention (the laminate of the present invention) may include layers other than those described above. It is preferable that the glass substrate and the adhesive layer are in contact in at least a portion (preferably the entire surface of one side of the glass substrate). It is also preferable that the adhesive layer and the decorative layer are in contact in at least a portion (preferably the entire surface of one side of the decorative layer).

[0116] Figures 4 to 13 show cross-sectional views of one embodiment of the laminate of the present invention. The laminate 1 shown in Figure 4 comprises a glass substrate 2, an adhesive layer 3, and a decorative layer 4. The glass substrate 2 is chemically strengthened glass or alkali-free glass. The adhesive layer 3 is formed on a part of the glass substrate 2 so as to be in contact with the glass substrate 2. The shape of the adhesive layer 3 is not particularly limited, but for example, in the view of preventing light from entering the interior when the decorative layer 4 has light-shielding properties, it is formed in a frame shape (annular, picture frame shape, etc.) along the edge of the glass substrate 2. The adhesive layer 3 only needs to be formed on at least a part of the side of the glass substrate 2 where the decorative layer 4 is located, and may be formed on the entire surface of the side of the glass substrate 2 where the decorative layer 4 is located.

[0117] The decorative layer 4 is laminated via the adhesive layer 3. In other words, the decorative layer 4 is laminated on top of the adhesive layer 3. Preferably, the area where the decorative layer 4 is formed is the same area as the area where the adhesive layer 3 is formed, or it is inside the area where the adhesive layer 3 is formed. From the viewpoint of improving the adhesion of the decorative layer 4 to the glass substrate 2 and more reliably preventing the decorative layer 4 from falling off, it is preferable that the area where the decorative layer 4 is formed is inside the area where the adhesive layer 3 is formed. The shape of the decorative layer 4 is not particularly limited, but for example, if the decorative layer 4 has light-shielding properties, from the viewpoint of preventing light from entering the interior, it is formed in a frame shape (ring-shaped, picture frame-shaped, etc.) along the edge of the glass substrate 2.

[0118] The adhesive layer 3 contains a heat-transferable resin. Because the adhesive layer 3 contains a heat-transferable resin, the adhesive layer 3, which is made on a temporary substrate separate from the glass substrate 2, can be formed by heating and transferring it onto the glass substrate 2, resulting in excellent adhesion to the glass substrate 2. The decorative layer 4 also contains a heat-transferable resin. Because the decorative layer 4 contains a heat-transferable resin, the decorative layer 4, which is made on a temporary substrate separate from the glass substrate 2, can be formed by heating and transferring it to the adhesive layer 3. Furthermore, because both the adhesive layer 3 and the decorative layer 4 contain a heat-transferable resin, when the adhesive layer 3 is heat-transferred onto the decorative layer 4, or when the laminate of the adhesive layer 3 and the decorative layer 4 is transferred onto the glass substrate 2, the area near the boundary between the decorative layer 4 and the adhesive layer 3 becomes compatible, resulting in excellent adhesion between the adhesive layer 3 and the decorative layer 4, and consequently, excellent adhesion of the decorative layer 4 to the glass substrate 2.

[0119] In the laminate of the present invention, the decorative layer may be a single layer or a multi-layered layer. By forming a multi-layered layer, a thicker decorative layer can be created, and if the decorative layer has light-shielding properties, the light-shielding properties can be made even higher. Laminate 1 shown in Figure 5 is the same as laminate 1 shown in Figure 4, except that the decorative layer 4 is a multi-layered layer. When the decorative layer 4 is a multi-layered layer, the thickness and formation area of ​​the multiple decorative layers 4 may be the same or different. In laminate 1 shown in Figure 5, the multi-layered decorative layer 4 is stepped, and the formation area of ​​the first decorative layer from the adhesive layer 3 side is larger than the formation area of ​​the second decorative layer. With such a structure, the shape of the decorative layer 4 becomes more stable.

[0120] In the laminate of the present invention, the adhesive layer only needs to be laminated on at least a part of the substrate, and may be laminated on a part as shown in Figure 4, or on the entire surface as shown in Figure 6. The laminate 1 shown in Figure 6 is the same as the laminate 1 shown in Figure 1, except that the adhesive layer 3 is formed on the entire surface (one surface) of the glass substrate 2 on the side where the decorative layer 4 is located.

[0121] The laminate of the present invention may comprise multiple adhesive layers. For example, the laminate of the present invention comprises at least one adhesive layer on one side of the substrate (the side with the decorative layer), but may also comprise an adhesive layer on the side of the substrate opposite to the aforementioned side (the other side). The multiple adhesive layers may have the same thickness, composition, shape, or physical properties, or they may be different layers.

[0122] The laminate 1 shown in Figure 7 comprises multiple adhesive layers 3, with adhesive layer 31 and adhesive layer 32. In the laminate 1 shown in Figure 7, adhesive layer 31 is formed over the entire surface of one side of the glass substrate 2, and adhesive layer 32 is also formed on the other side of the glass substrate 2. Although adhesive layer 32 is formed over the entire surface of the other side of the glass substrate 2, it may also be formed on a portion of the other side of the glass substrate 2. Furthermore, in Figure 7, adhesive layer 31 may also be formed on a portion of one side of the glass substrate 2.

[0123] In the laminate 1 shown in Figure 8, the adhesive layer 3 is formed over the entire surface of one side of the glass substrate 2 and is formed to cover the decorative layer 4. As shown in Figure 8, the decorative layer may also be covered by the adhesive layer.

[0124] The laminate of the present invention may have an adhesive layer on one of the above-mentioned surfaces (the surface on which the adhesive layer and the decorative layer are provided). The adhesive layer is preferably formed to be in contact with at least one of the adhesive layer and the decorative layer, and is preferably formed to be in contact with at least the adhesive layer from the viewpoint of having superior adhesive properties of the adhesive layer to the substrate. In particular, it is more preferable that the adhesive layer is formed to cover both the adhesive layer and the decorative layer from the viewpoint of more reliably preventing the decorative layer from falling off. Furthermore, the adhesive layer is preferably provided on at least a part of the substrate, and may be provided on the entire surface of the substrate.

[0125] The laminate 1 shown in Figure 9 comprises an adhesive layer 5. The adhesive layer 5 is formed to cover the entire surface of one of the glass substrates 2, including the adhesive layer 3 and the decorative layer 4. The adhesive layer 5 is in contact with both the adhesive layer 3 and the decorative layer 4.

[0126] The laminate 1 shown in Figure 10 is the same as the laminate 1 shown in Figure 9, except that the adhesive layer 3 is formed over the entire surface of one of the glass substrates 2. As shown in Figure 10, the adhesive layer 3 is provided over the entire surface of the glass substrate 2, which further increases the adhesion of the adhesive layer 5 to the glass substrate 2.

[0127] The laminate 1 shown in Figure 11 is the same as the laminate 1 shown in Figure 7, except that the adhesive layer 3 is formed over the entire surface of one side of the glass substrate 2 and covers the decorative layer 4. When the adhesive layer 3 covers the decorative layer 4 as shown in Figure 11, there is no area where the adhesive layer 5 and the decorative layer 4 come into contact, and the adhesion of the adhesive layer 5 to the glass substrate 2 becomes even higher.

[0128] The laminate of the present invention may comprise a plurality of adhesive layers. For example, the laminate of the present invention may have an adhesive layer on one side of the substrate (the side with the decorative layer), on the other side of the substrate, or on both sides. The plurality of adhesive layers may have the same thickness, composition, shape, or physical properties, or they may be different layers.

[0129] Furthermore, from the viewpoint of having superior adhesion to the substrate, it is preferable that at least a portion of the adhesive layer provided on the other surface is provided via the adhesive layer provided on the other surface.

[0130] The laminate 1 shown in Figure 12 comprises a plurality of adhesive layers 5, with adhesive layer 51 and adhesive layer 52. Adhesive layer 52 is provided via an adhesive layer 32 formed on the entire surface of the other side of the glass substrate 2. Other aspects are the same as the laminate shown in Figure 10. In the laminate 1 shown in Figure 12, the adhesive layer 32 is formed on the entire surface of the other side of the glass substrate 2, but it may also be formed on a part of the other side of the glass substrate 2. Also, in Figure 12, adhesive layer 31 may be formed on a part of one side of the glass substrate 2.

[0131] In the laminate 1 shown in Figure 13, the adhesive layer 31 is formed over the entire surface of one side of the glass substrate 2 and is also formed to cover the decorative layer 4. Other aspects are the same as those of the laminate 1 shown in Figure 12.

[0132] Furthermore, the laminate of the present invention may have a protective layer and a receiving layer on the decorative layer. If a protective layer and a receiving layer are present, they are laminated in this order on the decorative layer. Also, if the laminate of the present invention includes an adhesive layer, the protective layer and the receiving layer are laminated between the decorative layer and the adhesive layer.

[0133] The haze value (H) of the region of the laminate of the present invention in which the decorative layer is not laminated is not particularly limited, but from the viewpoint of efficiently reducing color shift and interference unevenness of the OLED display device, it is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less. Furthermore, although the above haze value is not particularly limited, it may be, for example, 0.01% or more, or 0.05% or more. It is preferable that the haze value in the region of the laminate in which the decorative layer is not laminated, which includes chemically strengthened glass or alkali-free glass as a substrate, and in which one end face (for example, the end face of the one surface) is an adhesive layer or tack layer provided on one surface of the substrate, and the other end face (for example, the end face of the other surface) is the substrate, or an adhesive layer or tack layer provided on the other surface of the substrate, is within the above range.

[0134] The total light transmittance of the laminate of the present invention in the region where the decorative layer is laminated is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less, from the viewpoint of ensuring concealment by the decorative layer. Furthermore, the above total light transmittance is not particularly limited, but may be, for example, 0.00001% or more, or 0.0001% or more. It is preferable that the total light transmittance of a laminate containing chemically strengthened glass or alkali-free glass as a base material, wherein one end face (for example, the end face of the one surface) is a decorative layer, adhesive layer, or tack layer provided on one surface of the base material, and the other end face (for example, the end face of the other surface) is the base material, or an adhesive layer or tack layer provided on the other surface of the base material, is within the above range.

[0135] The total light transmittance of the laminate of the present invention in the region where no decorative layer is laminated is not particularly limited, but from the viewpoint of ensuring the brightness of the OLED display device, it is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. Furthermore, although the above total light transmittance is not particularly limited, it may be less than 100%, 99.9% or less, or 99% or less. It is preferable that the total light transmittance of the laminate, which includes chemically strengthened glass or alkali-free glass as a substrate, has one end face (for example, the end face of the one surface) as an adhesive layer or tack layer provided on one surface of the substrate, and the other end face (for example, the end face of the other surface) as the substrate, or an adhesive layer or tack layer provided on the other surface of the substrate, be within the above range.

[0136] The haze value and total light transmittance of the laminate of the present invention can be measured by the methods specified in JIS K7136 and JIS K7361, respectively, and can be controlled by the type and thickness of each layer constituting the laminate.

[0137] The applications of the laminate of the present invention are not particularly limited and can be used for any purpose. Preferably, the laminate of the present invention is a laminate that can be used for optical applications, that is, for lamination on optical members (optical laminate). Examples of the optical members include electrical and electronic equipment. Note that "electrical and electronic equipment" refers to equipment that falls under at least one of electrical equipment or electronic equipment. Examples of the electrical and electronic equipment include image display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, and portable electronic devices. Examples of the image display devices include image display devices in portable electronic devices and displays (roll displays) inside and outside vehicles such as trains and buses.

[0138] Examples of the above-mentioned image display devices include liquid crystal displays, organic / inorganic electroluminescent displays, plasma displays, and OLED display panels. Examples of the above-mentioned image display devices include image display devices in portable electronic devices, in-vehicle displays, and digital signage (electronic billboards). The above-mentioned image display devices may be in the form (structure) of a so-called "flexible type," or they may be in the form (structure) of a so-called "foldable type" or "rollable type," which can be bent or folded.

[0139] Examples of the above-mentioned portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices (for example, wristwear-type devices worn on the wrist like watches, modular-type devices attached to a part of the body with clips or straps, eyewear-type devices including glasses (monocular and binocular types, including head-mounted types), clothing-type devices attached to shirts, socks, hats, etc. as accessories, earwear-type devices attached to the ears like earphones, etc.), digital cameras, digital video cameras, audio equipment (portable music players, IC recorders, etc.), calculators (calculators, etc.), portable game consoles, electronic dictionaries, electronic organizers, e-books, in-car information systems, portable radios, portable televisions, portable printers, portable scanners, portable modems, etc. In this specification, "portable" means not merely being able to carry something, but having a level of portability that allows an individual (a typical adult) to carry it relatively easily.

[0140] The optical components mentioned above specifically include, for example, components and modules that make up portable electronic devices, and housings for components and modules that make up portable electronic devices. More specifically, they include cover glass, lenses (especially glass lenses), touch panels, touch sensors such as touch sensor films (especially touch sensor films with metal wiring such as metal mesh films and silver nanowire films), polarizing films, display panels, sheet keyboards, protective panels for information display sections, housings, decorative sheets, etc. In this specification, a display panel refers to a structure that consists of at least a lens (especially a glass lens) and a touch panel. Furthermore, the term "lens" in this specification is a concept that includes both transparent materials that exhibit light refraction and transparent materials that do not exhibit light refraction. In other words, the term "lens" in this specification also includes simple window panels that do not exhibit light refraction.

[0141] The laminate of the present invention can suitably use chemically strengthened glass or alkali-free glass, which is thin and has excellent flexibility and impact resistance, as the substrate. Therefore, the laminate of the present invention is preferably used for lamination to components in electrical and electronic equipment that is used in a bendable manner, such as a bendable substrate, such as a bendable image display device (flexible display) (especially a foldable image display device (foldable display)).

[0142] The laminate of the present invention is preferably used by being laminated onto an OLED display panel. The OLED display panel comprises at least an OLED element in which an anode, an OLED layer including an emissive layer, and a cathode are laminated in that order. The laminate of the present invention is laminated on the viewing side of the OLED element in the OLED display panel. An OLED display device in which the laminate of the present invention and the OLED display panel are laminated may be referred to as "the OLED display device of the present invention".

[0143] The laminate of the present invention is preferably a laminate used in an OLED display device in which only optical elements with a polarization degree of 95% or less are laminated on the viewing side of the OLED element (laminated for OLED display device). That is, in the OLED display device of the present invention, it is preferable that only optical elements with a polarization degree of 95% or less are laminated on the viewing side of the OLED element in the OLED display panel. "Only optical elements with a polarization degree of 95% or less are laminated on the viewing side of the OLED element" means that the optical elements on the viewing side of the OLED element do not include optical elements with a polarization degree exceeding 95%. "Optical elements with a polarization degree exceeding 95%" are not particularly limited, but include polarizers such as linear polarizers, quarter phase difference plates, half phase difference plates, circular polarizers, and reflective polarizers. That is, in the OLED display device of the present invention is preferably an OLED display device that does not include polarizers on the viewing side of the OLED element.

[0144] The degree of polarization is determined by the following formula, based on the parallel transmittance Tp and orthogonal transmittance Tc, which are measured using a UV-Vis spectrophotometer and corrected for luminous sensitivity. Polarization degree (%)={(Tp-Tc) / (Tp+Tc)}1 / 2×100

[0145] The OLED display device of the present invention, by not including a polarizing plate on the viewing side of the OLED element, suppresses the absorption of light emitted from the OLED element by the polarizing plate, improving light collection efficiency, saving power consumption, and extending the lifespan of the OLED element. Furthermore, the absence of a polarizing plate allows for a thinner design and reduces manufacturing costs.

[0146] The embodiments described above are provided to facilitate understanding of the present invention and are not intended to limit it. [Examples]

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0148] Example 1 (Formation of adhesive sheet) An epoxy solution was prepared by adding 50 parts by mass of 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (trade name "Celoxide EHPE3150", manufactured by Daicel Corporation) and 100 parts by mass of ethyl acetate as epoxy polymers and stirring. To the above epoxy solution, an acrylic polymer, a methyl ethyl ketone solution of acrylic resin (solids content 40% by weight, trade name "KRM-9322", manufactured by Daicel Ornex Corporation), was added so that the solids content was 50 parts by mass and the mixture was stirred. To this solution, 5 parts by mass of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate (trade name "CPI-110P", manufactured by Sunapro Co., Ltd.) as a photoacid generator, 1 part by mass of a photoradical generator (trade name "Omnirad 651", manufactured by IGM Resins Italia Srl), 1 part by mass of another photoradical generator (trade name "Omnirad 184", manufactured by IGM Resins Italia Srl), and 428 parts by mass of ethyl acetate were added and stirred to obtain an adhesive solution. The above adhesive solution was applied to the other side of a polyester film (trade name "Lumirror 5AF531", manufactured by Toray Industries, Inc.) opposite to the side with the heat-resistant coating to form an adhesive layer with a thickness of 2 μm, and dried at 80°C for 1 minute to produce an adhesive sheet.

[0149] (Preparation of temporary substrate with adhesive layer and decorative layer) Using the above-mentioned adhesive sheet and a thermal printer ink ribbon (product name "BLACK", manufactured by SGJ Corporation, with a decorative layer thickness of 1 μm) equipped with a base film as a decorative layer, a thermal printer (product name "MDD7H system", manufactured by SGJ Corporation) was used to continuously transfer print the above decorative layer and the above adhesive layer onto a polyester film (product name "Lumirror S10", manufactured by Toray Industries, Inc.) as a temporary substrate, thereby obtaining a temporary substrate with adhesive and decorative layers. The transport speed of the polyester film during transfer was 1 inch / second, the transfer power for the decorative layer was 90 mW / dot, and the transfer power for the adhesive layer was 45 mW / dot.

[0150] (Fabrication of laminates) A thermal roll laminating machine (product name "MRK-600A modified", manufactured by MCK Corporation) was used to thermal laminate a temporary substrate with an adhesive layer and a decorative layer onto a glass substrate, which was chemically strengthened glass (product name "T2X-1", manufactured by Nippon Electric Glass Co., Ltd., 70 mm wide, 160 mm long, 0.035 mm thick). The thermal lamination was performed at a temperature of 150°C and a conveying speed of 0.5 mm / min. After thermal lamination, the polyester film was removed to obtain the laminate of Example 1 having a laminated structure of [glass substrate / adhesive layer / decorative layer].

[0151] Example 2 In the fabrication of the laminate, the laminate was prepared in the same manner as in Example 1, except that the glass substrate was changed to (product name "Gorilla Glass 3", manufactured by Matsunami Glass Industry Co., Ltd., 200 mm wide, 300 mm long, 1 mm thick).

[0152] Comparative Examples 1 and 2 In the preparation of the temporary substrate with adhesive layer and decorative layer, an adhesive sheet was not used, and only the decorative layer was transferred to obtain a temporary substrate with a decorative layer. The laminates of Comparative Examples 1 and 2, having a laminated structure of [glass substrate / decorative layer], were prepared in the same manner as in Examples 1 and 2, except that this temporary substrate with a decorative layer was used instead of the temporary substrate with adhesive layer and decorative layer.

[0153] [evaluation] The laminates obtained in the examples and comparative examples were evaluated as follows, and the results are shown in Table 1.

[0154] (1) Transferability In the above examples and comparative examples, the transferability was visually evaluated based on the area of ​​the adhesive layer transferred to the glass substrate after peeling off the polyester film following heat lamination. When the total area of ​​the adhesive layer to be transferred was set to 100%, a transfer rate of 95% or more of the adhesive layer to the glass substrate was marked as "○", a transfer rate of 80% or more but less than 95% was marked as "△", and a transfer rate of less than 80% was marked as "×".

[0155] (2) Adhesion A cross-cut test was conducted using the laminate prepared in the above example. Six vertical and horizontal cuts were made with a cut interval of 2 mm to form a grid pattern of 25 squares. Adhesive tape (product name "Sellotape", manufactured by Nichiban Co., Ltd.) was applied to the grid pattern and peeled off at an angle of approximately 60° at a speed of 0.5 to 1 second. When peeled, "○" was used if no peeling occurred in any of the grids, "△" was used if peeling of the adhesive layer or decorative layer occurred but the peeled area was less than 5%, and "×" was used if peeling of 5% or more of the adhesive layer or decorative layer occurred. Furthermore, for comparative examples where the transferability was marked "×" in the above transferability evaluation, adhesion evaluation was not performed. In addition, the back of the glass was backed with adhesive tape (product name "No31B", manufactured by Nitto Denko Corporation) as needed for evaluation.

[0156] [Table 1]

[0157] The method described in the example allowed for the continuous production of a laminate with a [glass substrate / adhesive layer / decorative layer] structure, enabling efficient lamination of the decorative layer onto the glass substrate and resulting in excellent productivity. Furthermore, the produced laminate exhibited excellent adhesion between the decorative layer and the adhesive layer to the glass substrate. On the other hand, when the adhesive layer was not used, the decorative layer did not adhere to the glass substrate, making it impossible to produce the desired laminate (Comparative Examples 1 and 2).

[0158] The following describes variations of the invention relating to this disclosure. [Note 1] A method for manufacturing a laminate comprising a glass substrate, an adhesive layer laminated on at least a portion of the glass substrate, and a decorative layer formed to be in contact with the adhesive layer, A decorative layer transfer step in which the decorative layer formed on the film substrate (a) is heated and transferred to one side of the temporary substrate, A method for manufacturing a laminate, comprising at least an adhesive layer transfer step of heating the adhesive layer formed on a film substrate (b) and transferring it onto the decorative layer. [Note 2] The method for manufacturing a laminate according to Appendix 1, wherein in the adhesive layer transfer step, the adhesive layer is transferred so as to cover the decorative layer. [Note 3] A method for manufacturing a laminate according to Appendix 1 or 2, wherein the decorative layer transfer step and the adhesive layer transfer step are carried out in succession. [Note 4] A method for manufacturing a laminate according to any one of the appendices 1 to 3, comprising unwinding the temporary substrate from a wound body while performing the decorative layer transfer step and the adhesive layer transfer step, and winding the temporary substrate on which the decorative layer and the adhesive layer are laminated as a wound body. [Note 5] A method for manufacturing a laminate according to any one of the appendices 1 to 4, wherein the amount of heat used when heating the adhesive layer during the transfer process is less than the amount of heat used when heating the decorative layer during the transfer process. [Note 6] The temporary substrate comprises, in this order, a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer. A method for manufacturing a laminate according to any one of the appendices 1 to 5, wherein the decorative layer is transferred onto the receiving layer in the decorative layer transfer step. [Note 7] The one surface of the temporary substrate and the one surface of the glass substrate are placed facing each other, and the adhesive layer is brought into contact with the one surface of the glass substrate. A method for manufacturing a laminate according to any one of appendices 1 to 6, comprising a laminate transfer step of heat laminating the temporary substrate under pressure from the side on which the decorative layer and the adhesive layer are not laminated, thereby transferring the laminate of the decorative layer and the adhesive layer onto the glass substrate. [Note 8] The temporary substrate comprises, in this order, a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer. The method for manufacturing a laminate according to Appendix 7, wherein, in the laminate transfer step, the protective layer and the receiving layer in the temporary substrate are transferred onto the decorative layer together with the decorative layer and the adhesive layer when the decorative layer and the adhesive layer are transferred onto the glass substrate. [Explanation of symbols]

[0159] 1. Laminate 2 Glass substrate 3,31,32,3a Adhesive layer 4,4a Decorative layer 5, 51, 52 Adhesive layer 6. Film substrate (a) 7 Temporary base material 8. Heating jig 9 Film substrate (b) 10 Heating fixture 11 rolls

Claims

1. A method for manufacturing a laminate comprising a glass substrate, an adhesive layer laminated on at least a portion of the glass substrate, and a decorative layer formed to be in contact with the adhesive layer, A decorative layer transfer step in which the decorative layer formed on the film substrate (a) is heated and transferred to one side of the temporary substrate, A method for manufacturing a laminate, comprising at least an adhesive layer transfer step of heating the adhesive layer formed on a film substrate (b) and transferring it onto the decorative layer.

2. The method for manufacturing a laminate according to claim 1, wherein the adhesive layer is transferred in the adhesive layer transfer step so as to cover the decorative layer.

3. A method for manufacturing a laminate according to claim 1 or 2, wherein the decorative layer transfer step and the adhesive layer transfer step are performed in succession.

4. A method for manufacturing a laminate according to claim 1 or 2, comprising unwinding the temporary substrate from a wound body while performing the decorative layer transfer step and the adhesive layer transfer step, and winding the temporary substrate on which the decorative layer and the adhesive layer are laminated as a wound body.

5. A method for manufacturing a laminate according to claim 1 or 2, wherein the amount of heat used when heating the adhesive layer during the transfer of the adhesive layer is smaller than the amount of heat used when heating the decorative layer during the transfer of the decorative layer.

6. The temporary substrate comprises, in this order, a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer. A method for manufacturing a laminate according to claim 1 or 2, wherein the decorative layer is transferred onto the receiving layer in the decorative layer transfer step.

7. The one surface of the temporary substrate and the one surface of the glass substrate are placed facing each other, and the adhesive layer is brought into contact with the one surface of the glass substrate. A method for manufacturing a laminate according to claim 1 or 2, comprising a laminate transfer step of heat laminating the temporary substrate under pressure from the side on which the decorative layer and the adhesive layer are not laminated, thereby transferring the laminate of the decorative layer and the adhesive layer onto the glass substrate.

8. The temporary substrate comprises, in this order, a plastic film, a release layer laminated on one side of the plastic film, a protective layer, and a receiving layer. The method for manufacturing a laminate according to claim 7, wherein in the laminate transfer step, the protective layer and the receiving layer in the temporary substrate are transferred onto the decorative layer together with the decorative layer and the adhesive layer when the decorative layer and the adhesive layer are transferred onto the glass substrate.

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